RU2714081C2 - Method of producing article from foamed polyurethane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing an article from foamed polyurethane. Method includes a step for producing a resin composition after two months or more after obtaining a recycled composition and providing a resin composition in a vessel containing a recycled resin composition to form a mixture of resin compositions. Resin composition contains a polyol component containing one or more polyether polyols of sucrose/glycerine, an amine catalyst and a pore-forming component. Porous component includes hydrofluoroolefin and formic acid. Method also includes steps of combining a resin composition, a recycled resin composition and an isocyanate component to form a reaction mixture and unloading the reaction mixture to form an article of foamed polyurethane. Recycled resin composition is present in the mixture of resin compositions in amount of 0.1–10 wt. % in terms of the total weight of the mixture of resin compositions. Mixture of resin compositions and isocyanate component are combined in weight ratio from 0.6:1 to 1.1:1.

EFFECT: technical result is prevention of moisture infiltration and growth of mold and reduced costs for heating and cooling in insulating articles from foamed polyurethane, functioning as a seamless and maintenance-free air barrier.

15 cl, 2 tbl

Description

The object of the invention relates generally to a method for producing a product from polyurethane foam. More specifically, an object of the invention relates to a method for producing products from polyurethane foam containing the product of the interaction of the resin composition and isocyanate.

In the construction industry, transport and the industry of household appliances and machines, polyurethane foam is used to isolate structures. As an insulation, polyurethane foam functions as a seamless and maintenance-free air barrier that provides many benefits, such as preventing moisture infiltration and mold growth and reducing energy consumption, for example, reducing heating and / or cooling costs.

As is also known in the art, polyurethane foam is formed as a result of an exothermic reaction of the resin composition and the isocyanate component, i.e. polyurethane system. From a commercial point of view, the resin composition, which includes a mixture of polyols, blowing agents, catalysts and other components, is supplied as a first component, for example, as an A-side component. The isocyanate component that interacts with the resin composition is supplied as a second component, for example, an Extraneous component. The resin composition includes various components, for example, reagents, catalysts, blowing agents, which can interact over time and reduce the shelf life of the resin composition or prevent its reuse. Therefore, the resin composition and the isocyanate component are selected to optimize storage stability, consumer properties and the ability to reuse the polyurethane system, as well as to optimize the operational properties of the polyurethane foam product for a specific application.

A method of obtaining a product from polyurethane foam includes the step of obtaining a resin composition. The resin composition includes a polyol component, an amine component and a pore-forming component. The pore-forming component includes hydrofluoroolefin and formic acid. The method also includes the steps of combining the resin composition, the recycled resin composition and the isocyanate component to form a reaction mixture and discharging the reaction mixture to form a polyurethane foam article.

A polyurethane system, a method for producing a product from polyurethane foam using a polyurethane system, and a product from polyurethane foam are disclosed. A polyurethane foam article according to the present invention is typically used to isolate structures. As an insulation, a polyurethane foam product functions as a seamless and maintenance-free air barrier that provides many benefits, such as preventing moisture infiltration and mold growth and reducing heating and cooling costs. A polyurethane foam article is formed using a polyurethane system containing a resin composition, a pore-forming component and an isocyanate component. A polyurethane system is chosen to optimize the efficiency of use and the performance of a polyurethane foam product for a particular application. For example, in the case of using a polyurethane foam product to isolate structures, the components of the polyurethane system are chosen so as to optimize consumer and performance characteristics, for example, insulating, adhesive and other properties of the polyurethane foam product formed from it.

In various embodiments, the disclosure polyurethane system is described as a “foamed” foam system. In such embodiments, a “foamed foam composition” is obtained by combining a stream comprising a resin composition comprising one or more polyols, a pore-forming component and other additives, for example, from an A-sided vessel), with a stream containing an isocyanate component (for example, from a B-sided vessel), with the formation of a reaction mixture, where the pore-forming component evaporates sufficiently and spontaneously when the two combined streams are exposed to atmospheric pressure during discharge from the distribution head to obtain m of foam. Thus, the pore-forming component functions as a foaming agent. It should be understood that not all of the pore-forming component must be immediately evaporated from / in the reaction mixture during unloading, but at least an amount sufficient to produce foam when unloaded from the distribution head onto the substrate.

Now with reference to the specific components of the polyurethane system, the resin composition includes a polyol component, an amine catalyst and, if necessary, a recycled resin composition. In some embodiments, the resin composition also includes a pore-forming component. In many embodiments, the resin composition is an amber liquid having a viscosity of less than about 900, alternatively about 200 to about 800, alternatively about 300 to about 700, alternatively about 400 to about 600, alternatively about 450 to about 550 cps at 25 ° C.

In a typical embodiment, the mixture of the resin composition (which includes the resin composition, which may include the recycled resin composition forming the previous generation, and the combined recycled resin composition (for example, in an A-sided vessel, as described below), has a viscosity of less than about 900, alternatively from about 200 to about 800, alternatively from about 300 to about 700, alternatively from about 400 to about 600, alternatively from about 450 to about 550 cps at 25 ° C.

The resin composition includes a polyol as one component. The polyol component includes one or more polyols and typically includes a combination of polyols. A polyol includes one or more OH functional groups, typically at least two OH functional groups. Typically, the polyol is selected from simple polyether polyols, complex polyester polyols, simple / complex polyether polyols, biopolyols, and combinations thereof, however, other gender polyols can also be used. Various polyols and other components that can be included in the resin composition of the subject invention are set forth in US Pat. No. 6,553,556, which is incorporated herein by reference in its entirety.

In some embodiments, the polyol as one component is included in the resin composition in an amount of from about 30 to about 99, alternatively from about 40 to about 95, alternatively from about 50 to about 80, alternatively from about 60 to about 70 weight percent, based on the total weight of the resin composition. The amount of the polyol as one component may vary outside the above ranges, but as a rule is both integer and fractional values within these ranges. In addition, it should be appreciated that more than one polyol can be included in the polyol component, in which case the total number of all included polyols is within the above ranges.

In some embodiments, the polyol component comprises one or more polyether polyols. In such embodiments, the polyol component comprises one or more sucrose / glycerol polyether polyols, i.e. a polyol formed with initiator sucrose and / or glycerol.

In some embodiments, the polyol component comprises a first polyether polyol. The first polyether polyol is formed from sucrose and / or glycerol initiator. The first polyol typically has: an average molecular weight of from about 400 to about 800, alternatively from about 500 to about 700 g / mol; a hydroxyl number from about 300 to about 500, alternatively from about 350 to about 450 mg KOH / g; functionality of more than 3, alternatively from about 4 to about 5; and a viscosity of less than about 5000, alternatively from about 3000 to about 4000 cps at 25 ° C. Of course, the average molecular weight, hydroxyl number, functionality and viscosity of the first simple polyether polyol can be any value or range of values, either integer or fractional, within these ranges and the values described above, and / or can vary from and / or ranges of values are ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, ± 30%, etc.

In some embodiments, the resin composition comprises from about 40 to about 50, alternatively from about 30 to about 60 weight percent of the first polyether polyol, based on the total weight of the polyol component. The amount of the first simple polyether polyol can vary outside the above ranges, but as a rule it is both integer and fractional values within these ranges.

In some embodiments, the polyol component comprises a second polyether polyol. A second polyether polyol is also formed from sucrose and / or glycerol initiator. The second simple polyether polyol typically has: an average molecular weight of from about 500 to about 800, alternatively from about 600 to about 700 g / mol; a hydroxyl number from about 300 to about 600, alternatively from about 400 to about 500 mg KOH / g; functionality of more than 4, alternatively from about 5 to about 6; and a viscosity of more than about 15,000, alternatively more than about 30,000, alternatively from about 15,000 to about 40,000, alternatively from about 30,000 to about 40,000 cps at 25 ° C. Of course, the average molecular weight, hydroxyl number, functionality and viscosity of the second polyether polyol can be any value or range of values, either integer or fractional, within these ranges and the values described above, and / or can vary from and / or ranges of values are ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, ± 30%, etc.

In some embodiments, the resin composition comprises from about 5 to about 40, alternatively from about 10 to about 20 weight percent of the second polyether polyol, based on the total weight of the polyol component. The amount of the second polyether polyol can vary outside the above ranges, but as a rule is both integer and fractional values within these ranges.

In some embodiments, the polyol component comprises a third polyether polyol. The third simple polyether polyol typically has: an average molecular weight of from about 500 to about 900, alternatively from about 600 to about 800 g / mol; a hydroxyl number from about 100 to about 400, alternatively from about 200 to about 300 mg KOH / g; functionality of more than 2, alternatively from about 2 to about 4; and a viscosity of less than about 500, alternatively from about 100 to about 300 cps at 25 ° C. Of course, the average molecular weight, hydroxyl number, functionality and viscosity of the third simple polyether polyol can be any value or range of values, either integer or fractional, within these ranges and the values described above, and / or can vary from and / or ranges of values are ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, ± 30%, etc.

In some embodiments, the resin composition comprises from about 5 to about 40, alternatively from about 10 to about 20 weight percent of the third polyether polyol, based on the total weight of the polyol component. The amount of the third simple polyether polyol can vary outside the above ranges, but as a rule is both integer and fractional values within these ranges.

In some embodiments, the polyol component comprises a polyester polyol. The polyester polyol is typically an aromatic polyester polyol. The polyester polyol typically has: an average molecular weight of from about 500 to about 900, alternatively from about 600 to about 800 g / mol; a hydroxyl number from about 100 to about 400, alternatively from about 200 to about 300 mg KOH / g; functionality of more than 2, alternatively from about 2 to about 3; and a viscosity of from about 1500 to about 15000, alternatively from about 4000 to about 15000, alternatively from about 6000 to about 15000, alternatively from about 8000 to about 14000, alternatively from about 10,000 to about 14000 cps at 25 ° C. Of course, the average molecular weight, hydroxyl number, functionality and viscosity of the polyester polyol can be any value or range of values, either integer or fractional, within these ranges and the values described above, and / or can vary from the values and / or ranges of values are ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, ± 30%, etc.

In some embodiments, the resin composition comprises from about 5 to about 50, alternatively from about 15 to about 25 weight percent polyester polyol, based on the total weight of the polyol component. The amount of polyester polyol can vary outside the above ranges, but as a rule is both integer and fractional values within these ranges.

In some embodiments, the polyol component comprises biologically derived polyol, such as glycerin or castor oil. As demonstrated above, the average molecular weight, hydroxyl number, and polyol functionality may vary. As such, the polyols referenced above are illustrative in nature and are not regarded as limiting.

In various preferred embodiments, the polyol component comprises a first polyether polyol and a second polyether polyol. In such embodiments, the first and second polyether polyols are present in a ratio of from about 1: 1 to about 5: 1, alternatively from about 1: 2 to about 1: 4. In such preferred embodiments, the polyol component may also include a third polyether polyol and polyester polyol.

In many embodiments, the resin composition comprises a recycled resin composition. The recycled resin composition is a component of the resin composition and is different from it. In the broadest sense, a recycled resin composition can be defined as any resin composition that was obtained before the resin composition in which it is included. As such, the recycled resin composition is any unused or excess resin composition that was obtained before the resin composition was prepared. In some embodiments, a recycled resin composition is formed of more than about 2, alternatively more than about 3, alternatively more than about 4, alternatively more than about 5, alternatively more than about 6, alternatively more than about 7, alternatively more than about 8, alternatively more than about 9 months before the formation of the resin composition, i.e. before the stage of mixing the components of the resin composition together with the formation of the resin composition. By way of example, the recycled resin composition may be an unused resin composition that remains in an A-sided vessel when the vessel is refilled with a “new” or “fresh” resin composition. In other words, the recycled resin composition may be the excess resin composition from a previous application of an A-sided vessel, the use of which is environmentally and commercially economical.

In many embodiments, one or more generations of the recycled resin composition may be included in the resin composition. For example, the resin composition and the recycled resin composition can be mixed and delivered to the consumer in an A-sided vessel. This mixture may be referred to as a “resin composition mixture”. After a single use, the A-sided vessel returns with a mixture of the resin composition and the recycled resin composition remaining in the A-sided vessel. After a single return, the resin composition is simply a “recycled resin composition”, which includes, in this example, two generations of the recycled resin composition, i.e., two different generations of the previously obtained resin composition. The resin composition can be formed and then combined with this recycled resin composition and delivered to the consumer in an A-sided vessel. After a single combining, this A-sided vessel includes two generations of recycled resin. Such recycling can continue and continue using multiple generations of recycled resin included in the A-sided vessel. In such a situation, the amount of each progressive generation of the resin composition, which is recycled and delivered in an A-sided vessel, becomes smaller and smaller. In the end, equilibrium is achieved with respect to the amount of recycled resin that is combined with the resin composition and, in this example, is included in an A-sided vessel. In other words, the amount of recycled resin that is combined with the resin composition (fresh resin) in an A-sided vessel is stabilized.

The recycled sample outlined in the previous paragraph is illustrative in its characteristics. The recycled resin composition can also be generated as the “remaining” or “excess” resin composition, which is obtained in industrial processes for preparing the resin composition and filling the vessels. Similar to the situation above, the recycled resin composition generated in industrial processes becomes a recycled resin composition that can be mixed with another “fresh” portion of the resin composition.

Advantageously, the resin composition is formulated so that the mixture of the resin composition and the recycled resin composition (e.g., the mixture of resin compositions) has an excellent shelf life. That is, a mixture of resin compositions (including one or more generations of recycled resin) exhibits compatible process characteristics and maintains compatible reactivity that allows for the compatible formation of a polyurethane foam product having excellent physical properties.

In some embodiments, the resin composition comprises from about 0.1 to about 10, alternatively from about 0.1 to about 8, alternatively from about 0.1 to about 6 weight percent of the recycled resin composition, based on the total weight of the resin composition. The amount of recycled resin composition may vary outside the above ranges, but as a rule is both integer and fractional values within these intervals. Additionally, as described above, it should be borne in mind that more than one type or generation of a recycled resin composition can be included in the resin composition, in which case the total amount of all included recycled resin composition is within the above ranges.

In various alternative embodiments, the resin composition and the recycled resin composition are separated from each other and combined later to form a mixture of resin compositions, and then the mixture of resin compositions and the isocyanate component (described below) are combined. In such embodiments, the mixture of resin compositions comprises from about 0.1 to about 10, alternatively from about 0.1 to about 8, alternatively from about 0.1 to about 6 weight percent of the recycled resin composition, based on the total weight of the resin compositions.

In other alternative embodiments, the resin composition, the recycled resin composition, and the isocyanate component are stored separately until the combining stage and subsequent production of the polyurethane foam article. In such embodiments, the resin composition comprises from about 0.1 to about 10, alternatively from about 0.1 to about 8, alternatively from about 0.1 to about 6 weight percent of the recycled resin composition based on the combined weight of the resin composition and the recycled resin composition . The amount of recycled resin composition may vary outside the above ranges, but as a rule is both integer and fractional values within these intervals. Additionally, it should be appreciated that more than one type of recycled resin composition can be used, in which case the total amount of the entire recycled resin composition is within the above ranges.

The resin composition includes a pore-forming component. The pore-forming component contains pore-forming agents that are included in the resin composition. The pore-forming component includes hydrofluoroolefin (HFO) and formic acid, and in many embodiments, the pore-forming component also includes water. In some embodiments, the pore-forming component is included in the resin composition in an amount of from about 1 to about 45, alternatively from about 5 to about 30, alternatively from about 10 to about 20 weight percent, based on the total weight of the resin composition. The amount of the pore-forming component may vary outside the above ranges, but as a rule it is both integer and fractional values within these intervals. Additionally, it should be appreciated that more than one blowing agent can be included in the pore-forming component, in which case the total number of all included blowing agents is within the above ranges.

As described above, the pore-forming component includes HFO. HFOs are chemical compounds containing hydrogen, fluorine and carbon atoms. HFOs are distinguished from hydrofluorocarbons (HFCs) in that they are derivatives of alkenes (olefins) and not alkanes. In some embodiments, the HFO is selected from the group of trans-1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, and combinations thereof. In a preferred embodiment, the HFO is or contains trans-1-chloro-3,3,3-trifluoropropene. In some embodiments, the blowing agent comprises from about 30 to about 95, alternatively from about 70 to about 90 weight percent HFO, for example, trans-1-chloro-3,3,3-trifluoropropene, based on the total weight of the blowing agent. The number of HFOs may vary outside of the above intervals, but as a rule are both integer and fractional values within these intervals.

HFOs are physical blowing agents. It is believed that the inclusion of one or more physical blowing agents in the pore-forming component lowers the thermal conductivity of the polyurethane foam coating. Physical blowing agents typically boil at an exothermic foaming temperature or less, preferably at about 50 ° C. or less. The resin composition may include additional physical blowing agents. Preferred additional physical blowing agents include those that have zero ozone depletion potential. Examples of physical blowing agents include volatile non-halogenated hydrocarbons containing from two to seven carbon atoms, such as alkanes, alkenes, cycloalkanes containing up to 6 carbon atoms, dialkyl ether, cycloalkylene esters and ketones, and HFC. Suitable additional physical blowing agents for the purpose of disclosing the subject of the invention may include HFC, chlorofluorocarbons (CFC), hydrocarbons, and combinations thereof.

The pore-forming component also includes formic acid, a chemical pore-forming agent. In some embodiments, the pore-forming component comprises from 1 to about 20, alternatively from about 5 to about 15 weight percent formic acid, based on the total weight of the pore-forming component. The amount of formic acid may vary beyond the above ranges, but as a rule is both integer and fractional values within these ranges. Formic acid, included in the pore-forming component, is believed to reduce the chemical interaction between HFO, such as trans-1-chloro-3,3,3-trifluoropropene, and the amine catalyst and the decomposition of the amine catalyst as a result of this interaction. Without being bound by theory, it is believed that the inclusion of formic acid in combination with the other claimed components increases the storage stability and recycling of the resin composition.

The resin composition may include additional chemical blowing agents. In many embodiments, the blowing agent also includes a chemical blowing agent, such as water. When water is included, the pore-forming component comprises from about 1 to about 20, alternatively from about 5 to about 15 weight percent water, based on the total weight of the pore-forming component. The amount of water can vary outside the above ranges, but as a rule it is both integer and fractional values within these intervals.

The resin composition includes one or more catalysts. The catalyst is typically present in the resin composition for catalyzing an exothermic reaction between the resin composition and the isocyanate. It should be appreciated that the catalyst is generally not consumed in the exothermic reaction between the resin composition and the isocyanate component. The catalyst may include any suitable catalyst or mixture of catalysts known in the art. Examples of suitable catalysts include, but are not limited to, gelation catalysts, for example, amine catalysts in dipropylene glycol; pore-forming catalysts, for example, bis (dimethylaminoethyl) ether in dipropylene glycol; and metal catalysts, for example, tin, bismuth, lead, etc. If included, the catalyst may be included in various amounts.

The resin composition typically includes an amine catalyst. Suitable amine catalysts for the purposes of the present invention include, but are not limited to, catalytic amines, such as primary, secondary and tertiary, cyclic and acyclic catalytic amines.

In addition to the catalyst, the resin composition optionally includes a surfactant. The surfactant typically supports the homogenization of the blowing agent and the polyol and regulates the porous structure of the polyurethane foam. The surfactant may include any applicable surfactant or mixture of surfactants known in the art. Non-limiting examples of suitable surfactants include various silicon-containing surfactants, sulfonic acid salts, for example, alkali metal and / or ammonium salts of oleic acid, stearic acid, dodecylbenzene or dinaphthalenemethane disulfonic acid and ricinoleinic acid, foam stabilizers, such as copolymers of siloxa-noxyalkylene and other organosiloxanes, ethoxylated alkyl phenols, ethoxylated fatty alcohols, paraffin oils, castor oil, complex esters ry castor oil and esters of ricin-leinovoy acid and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. In some embodiments, the surfactant has a viscosity of from about 300 to about 2500 cps at 25 ° C. In a preferred embodiment, the resin composition comprises a surfactant organosilicon copolymer having a viscosity of from about 1800 to about 2500 cps at 25 ° C. If included, the surfactant can be included in the resin composition in various amounts.

In addition to the surfactant, the resin composition optionally includes a flame retardant. The flame retardant may include any suitable flame retardant or a mixture of flame retardants known in the art. Non-limiting examples of useful flame retardants include tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate (TCP), tris (2,3-dibromopropyl) phosphate, red phosphorus, aluminum hydroxide, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, molybdenum trioxide, ammonium molybdate, ammonium phosphate, pentabromodiphenyl oxide, 2,3-dibromopropanol, hexabromocyclododecane, dibromethyldibromocyclohexane, expandable graphite or cyanuric acid derivatives, melamine and corn starch. In a preferred embodiment, the resin composition comprises TCP. In the presence of a flame retardant, various amounts may be included in the resin composition.

The resin composition optionally includes one or more additives. The additive may include any suitable additive or mixture of additives known in the art. Suitable additives for the purposes of this disclosure include, but are not limited to, chain extenders, dyes, indicator dyes, crosslinking agents, open circuit agents, processing aids, adhesion promoters, antioxidants, anti-foam additives, antifoam agents, water neutralizers, molecular sieves, highly dispersed silicon oxides , UV stabilizers, fillers, thixotropic additives, silicones, pigments, inert diluents and combinations thereof. Of course, additives also include catalysts and surfactants known in the art, but not described above. If included, the additive can be included in the resin composition in various quantities.

In various embodiments, the resin composition typically has a viscosity of less than about 900, alternatively about 300 to about 700, alternatively about 400 to about 600 cps at 25 ° C. As mentioned above, since the resin composition is chemically stable, it can be recycled, and it has an excellent shelf life. Shelf life can be defined as the period of life during which the resin composition produces foam having stable properties and / or the period of time during which the components of the resin composition are stable. From a practical point of view, the shelf life is a period of life during which the quality of the foam produced by the resin composition does not deteriorate to a predetermined extent (i.e., the foam produced by the resin meets certain quality requirements). In this regard, in many embodiments, the resin composition has a life of more than about 4, alternatively more than about 5, alternatively more than about 6, alternatively more than about 7, alternatively more than about 8 months when stored at 25 ° C. In other words, the resin composition can be stored for 4, 5, 6, 7, 8 or even more months, and its components, for example, an amine catalyst and trans-1-chloro-3,3,3-trifluoropropene, and other components , do not interact chemically or otherwise with a decrease in the reactivity of the resin and do not adversely affect the properties of the product made of polypenurethane formed from it.

The polyurethane system according to the present invention also includes an isocyanate component. The isocyanate component includes one or more types of isocyanate. Any combination of various types of isocyanates described in this description may be included in the isocyanate component. The isocyanate may be a polyisocyanate containing two or more functional groups, for example, two or more NCO functional groups. Suitable isocyanates for the purposes of this disclosure include, but are not limited to, aliphatic and aromatic isocyanates. In various embodiments, the isocyanate is selected from the group of diphenylmethanediisocyanates (MDI), polymeric diphenylmethanediisocyanates (pMDI), toluene diisocyanates (TDI), hexamethylene diisocyanates (HDI), isophorone diisocyanates (IPDI), and combinations thereof.

The isocyanate may be an isocyanate prepolymer. An isocyanate prepolymer is typically the product of the interaction of an isocyanate and a polyol and / or polyamine. The isocyanate used in the prepolymer may be any isocyanate described above. The polyol used to prepare the prepolymer is typically selected from the group of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, biopoliols, and combinations thereof. The polyamine used to prepare the prepolymer is typically selected from the group of ethylene diamine, toluene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines, amino alcohols, and combinations thereof. Examples of useful amino alcohols include ethanolamine, diethanolamine, triethanolamine, and combinations thereof.

Specific toluene diisocyanate; 4,4'-diphenylmethanediisocyanate; m-phenylenediisocyanate; 1,5-naphthalenediisocyanate; 4-chloro-1; 3-phenylenediisocyanate; tetramethylenediisocyanate; hexamethylene diisocyanate; 1,4-dicyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate, 2,4,6-toluylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate; 1-methyl-3,5-diethylphenylene-2,4-diisocyanate; 1,3,5-triethylphenylene-2,4-diisocyanate; 1,3,5-triisopropyl-phenylene-2,4-diisocyanate; 3,3-diethyl-bisphenyl-4,4'-diisocyanate; 3,5,3 ', 5'-tetraethyl diphenylmethane-4,4'-diisocyanate; 3,5,3 ', 5'-tetraisopropyl diphenylmethane-4,4'-diisocyanate; 1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate; 1,3,5-triethyl benzene-2,4,6-triisocyanate; 1-ethyl-3,5-diisopropyl benzene-2,4,6-triisocyanate; and 1,3,5-triisopropyl benzene-2,4,6-triisocyanate.

In a preferred embodiment, the isocyanate component comprises MDI and pMDI. In another preferred embodiment, the isocyanate component consists essentially of MDI and pMDI. In another preferred embodiment, the isocyanate component consists of MDI and pMDI. In many embodiments, the isocyanate component is a dark brown liquid having a viscosity of less than about 600, alternatively about 100 to about 500, alternatively about 100 to about 400, alternatively about 100 to about 300, alternatively about 150 to about 250 cps at 25 ° C.

Also, the disclosure of an object of the invention provides a method for producing a polyurethane foam product. A method of obtaining a product from polyurethane foam includes the steps of: obtaining a resin composition; combining the resin composition, the recycled resin composition and the isocyanate component to form a reaction mixture; and discharging the reaction mixture to form a polyurethane foam article. The resin composition, the recycled resin composition, and the isocyanate component are as described above.

In a preferred embodiment, the method includes the steps of providing a resin composition (including a recycled resin composition) in an A-sided vessel, providing an isocyanate component in a B-sided vessel, combining the resin composition with an isocyanate component to form a reaction mixture, and discharging the reaction mixture to form polyurethane foam. In various preferred embodiments, the A-side of the vessel has a pressure of less than about 700, alternatively from about 300 to about 600, alternatively from about 400 to about 600, alternatively from about 450 to about 550 lbs / inch ² (ang. Psi) at 25 ° C. In various preferred embodiments, the B-side of the vessel has a pressure of less than about 700, alternatively from about 300 to about 600, alternatively from about 400 to about 600, alternatively from about 450 to about 550 lb / ⁱⁿ² at 25 ° C.

In one embodiment, the unreacted resin composition and the isocyanate component are supplied in an A-sided and B-sided container, the components of which are collectively referred to as the polyurethane system and are as described above. Typically, an A-sided and B-sided container, i.e. polyurethane system, supplied together. The components of the polyurethane system are selected to ensure efficient use and the desired performance properties of the polyurethane foam product for a particular application. For example, in the case of using a polyurethane foam product to isolate structures, components of the polyurethane system are selected to provide a polyurethane system having reliable performance, stability of the resin composition and recycling, etc., and also selected to provide a polyurethane foam product having the desired insulating, adhesive and other properties.

In some embodiments, the method includes the step of mixing the polyol as one component, the amine catalyst, the recycled resin composition and the pore-forming component before the step of providing the resin composition in an A-sided vessel. In such embodiments, the recycled resin composition is formed in more than about 2, alternatively more than about 3, alternatively more than about 4, alternatively more than about 5, alternatively more than about 6, alternatively more than about 7, alternatively more than about 8, alternatively, more than about 9 months before the step of mixing the components of the resin composition together with the formation of the resin composition.

As also described above, the method also includes the step of combining the resin composition, the recycled resin composition and the isocyanate component. In a preferred embodiment, the method also includes the step of combining the resin composition comprising the recycled resin composition with an isocyanate component. In some embodiments, the combining step is further defined as combining the resin composition and the recycled resin composition first to form a mixture of resin compositions and then combining the mixture of resin compositions and the isocyanate component to form a reaction mixture. In a preferred embodiment, the method includes the step of heating the resin composition comprising the recycled resin composition (or a mixture of the resin compositions or each of the resin composition and the recycled resin composition) and the isocyanate to a temperature of from about 20 ° C to about 35 ° C, and more preferably to a temperature from about 24 ° C to about 30 ° C, before the step of combining the resin composition with the isocyanate in the presence of a blowing agent to form a reaction mixture. The resin composition and isocyanate can be combined by any mechanism known in the art to form a reaction mixture. Typically, the combining step is carried out in a mixing apparatus, such as a static mixer, a shock mixing chamber or a mixing pump. In a preferred embodiment, the combining step is carried out in a static mixing head. The combining step may include various processes known in the art, such as spraying or molding. In the case of molding, many embodiments of the polyurethane system are molded in a mold having a temperature of from about 25 to about 40 ° C.

Typically, the resin composition / polyol component and the isocyanate component are combined at an isocyanate index of from about 75 to about 140, alternatively from about 80 to about 130, alternatively from about 90 to about 130, alternatively from about 90 to about 120, alternatively from about 105 to about 120, alternatively from about 105 to about 115. In many embodiments, the resin composition and the isocyanate component are combined in a weight ratio of from about 0.6: 1 to about 1.1: 1.

As indicated above, the method includes the step of discharging the reaction mixture to form a polyurethane foam article. The reaction mixture can be discharged by various technologies, such as spraying, casting or molding. In some embodiments, the reaction mixture was discharged at a pressure of from about 150 to about 1000, alternatively from about 300 to about 600, alternatively from about 150 to about 600, alternatively from about 200 to about 300 lb / ^in2. In some embodiments, the reaction mixture is discharged at a rate of from about 1 to about 600, alternatively from about 1 to about 120, alternatively from about 1 to about 40, alternatively from about 3 to about 40, alternatively from about 4 to about 20, alternatively from about 6 to about 15 lb / min. It is contemplated that the reaction mixture can be discharged at any combination of pressures or velocities or pressure or velocity ranges within the ranges set forth above.

Like the components of a polyurethane system, a specific discharge / use technology is selected to optimize the efficiency of use and the performance of the polyurethane foam product for a particular application. Minor variations in the technology of use affect the operational properties of the product made of polyurethane foam. Therefore, for certain use technologies, certain recommendations are often made.

The invention also relates to a polyurethane foam article. In various embodiments, the polyurethane foam article has a total density of from about 1.8 to about 3, alternatively from about 1.6 to about 2.8, alternatively from about 2.3 to about 2.35 lb / ft ³ (pounds per cubic meter) ft.) and a core density of from about 1.9 to about 2.1, alternatively from about 1.9 to about 2.1, alternatively from about 1.95 to about 2.05 lb / ft ³ when tested in accordance with ASTM D-1622. In other embodiments, the article of the polyurethane foam has a resistance in the parallel direction of compression at 10% deflection of greater than about 10, alternatively from about 15 to about 45, alternatively from about 15 to about 25 lb / ^in2, and has a resistance in the perpendicular direction of compression at 10% rejection of greater than about 10, alternatively from about 10 to about 35, alternatively from about 15 to about 25 lbs / in ² when tested in accordance with ASTM D-1621.

As described above, a polyurethane foam article is often used as an insulating material. In this regard, many embodiments of the product made of polyurethane foam have an initial K-factor of less than about 0.25, alternatively less than about 0.16, alternatively less than about 0.13 BTU-inch / h / ft ² / ° F at testing in accordance with ASTM C-518. Additionally, many embodiments of a polyurethane foam article have a water absorption of less than about 0.1, alternatively less than about 0.03 lb / ft ^2, when tested in accordance with ASTM D-2842.

The polyurethane foam article may be a solid or flexible foam article, but typically it is a solid foam article. As such, the term “solid” foam typically includes flexible foams. Non-limiting examples of various physical properties that can be measured to characterize a solid foam product of many embodiments include density, compression resistance, compression modulus, air flow (lack thereof), elongation, tensile strength, etc. In some embodiments, it is understood that the term “solid foam” product describes a foam having a high ratio of compressive strength to tensile strength, for example, of about 0.5: 1 or more, and an elongation of about 10 percent or less. In some embodiments, the polyurethane foam article is a solid foam article having a closed pore content of more than about 80, alternatively more than about 85, alternatively more than about 90 percent of the closed pores.

The following example is intended to illustrate the invention and should not be construed in any way as limiting the scope of the invention.

EXAMPLE

The polyurethane foam of example 1 is presented in accordance with the present invention. As further described below, the Resin Composition 1 interacts with the Isocyanate Component 1 to form a polyurethane foam article of Example 1. The Resin Composition 1 is described immediately in Table 1 below.

Polyol A is a sucrose / glycerol-based polyether polyol having a nominal functionality of 4.0, a hydroxyl number of 368 mg KOH / g, and a viscosity of 3500 cps at 25 ° C.

Polyol B is a sucrose / glycerol-based polyether polyol having a nominal functionality of 5.5, a hydroxyl number of 470 mg KOH / g, and a viscosity of 35,000 cps at 25 ° C.

Polyol C is a modified aromatic polyester polyol having a nominal functionality of 2.3, a hydroxyl number of 258 mg KOH / g, and a viscosity of 12,000 cps at 25 ° C.

Polyol D is a glycerol-based trifunctional simple polyether polyol formed by adding propylene oxide to glycerol having a nominal functionality of 3, a hydroxyl number of 430 mg KOH / g, and a viscosity of 270 cPs at 25 ° C.

Fire retardant A is tris (1-chloro-2-propyl) phosphate.

Surfactant A is a silicon based copolymer surfactant.

Catalyst A is a pore-forming catalyst.

Catalyst B is a tertiary amine catalyst.

Catalyst C is a solution of sodium octoate in diethylene glycol.

Pore former A is formic acid.

Pore former B is water.

Pore former C is trans-1-chloro-3,3,3-trifluoropropene.

The isocyanate component A is a mixture of diphenylmethane di-zocyanate and polymer diphenylmethanediisocyanate.

Resin composition 1 and Isocyanate component 1 are heated to 80 ° F. Immediately after heating, the Resin composition 1 and the Isocyanate component 1 are combined in a mass ratio of 1: 1 to form a reaction mixture, which is discharged into a mold having a temperature of 90 ° C. The reaction mixture has a gel time of 80 seconds, a sticking time of 140 seconds, and a free foam density of 1.6 lb / ft ³ . Accordingly, a polyurethane foam article is formed according to Example 1. A test panel of 2 ft. X 2 ft. An X 2.5 inch containing a polyurethane foam article according to Example 1 is tested for various physical properties. The test results are presented below in table 2.

Advantageously, the resin composition 1 has a shelf life of more than 8 months. Additionally, the resin composition 1, which includes the content of the recycled resin, can be used to obtain products from polyurethane foam according to example 1, which exhibits excellent insulating and water-absorbing properties.

It should be understood that the appended claims are not limited in expressing particular compounds, compositions, or methods described in the detailed description, which may vary between specific embodiments that fall within the scope of the appended claims. With respect to any Markush groups justified here for describing specific features or aspects of various embodiments, it should be borne in mind that various special and / or unexpected results can be obtained for each element of the corresponding Markush group independently of other Markush elements. Each element of the Markush group can be justified individually and / or in combination and provides the necessary confirmation for specific embodiments within the scope of the attached claims.

It should also be understood that any intervals and subranges justified in the description of various embodiments of the present invention, independently and jointly fall within the scope of the attached claims, and it should be understood that they describe and include all intervals, including their integer and / or fractional values , even if such values are not spelled out here in a pronounced way. One skilled in the art can readily understand that the listed ranges and subranges sufficiently describe and provide a variety of embodiments of the present disclosure, and such ranges and subranges may be further expressed in terms of corresponding half fractions, tertiary fractions, quaternary fractions, fifth fractions and etc. As only one example, the interval "from 0.1 to 0.9" can be further subdivided into a lower third, i.e., from 0.1 to 0.3, an average third, i.e., from 0, 4 to 0.6, and the upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the attached claims, and can be justified individually and / or together, and provide the necessary confirmation for specific embodiments within the scope of the attached claims. In addition, with respect to linguistic forms that define or modify an interval, such as “at least”, “more than”, “less than”, “not more than”, etc., it should be understood that such a linguistic the form includes subranges and / or an upper or lower limit. As another example, the interval “at least 10” typically includes a sub-range of at least 10 to 35, a sub-range of at least 10 to 25, a sub-range of 25 to 35, etc., and each sub-range may be substantiated individually and / or jointly and provides the necessary confirmation for specific embodiments within the scope of the attached claims. Ultimately, an individual number within the disclosed interval can be justified and provides the necessary confirmation for specific embodiments within the scope of the attached claims. For example, the range "from 1 to 9" includes a variety of individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which can be justified and provide the necessary confirmation for specific embodiments within the scope of the attached claims.

The present invention is described in an illustrative manner and it should be understood that the terminology that has been applied is intended to be in the nature of the description words, and not limitation. Obviously, in the light of the above ideas, many modifications and variations of the present invention are possible. Therefore, it should be understood that within the scope of the attached claims, the present invention can be practiced in a manner other than specifically described.

Claims (27)

1. A method of producing a product from polyurethane foam, wherein said method comprises the steps of: obtaining a recycled resin composition, wherein the recycled resin composition is left in an A-sided vessel; obtaining a resin composition after two months or more after receiving a recycled resin composition, and the resin composition contains: (i) a polyol as one component comprising one or more sucrose / glycerol polyether polyols; (ii) an amine catalyst selected from the group consisting of primary amines, secondary amines and tertiary amines, cyclic amines and acyclic amines; and (iii) a blowing agent containing: (a) a hydrofluoroolefin selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene and combinations thereof, and (b) formic acid; providing a resin composition in an A-sided vessel comprising a recycled resin composition to form a mixture of resin compositions; providing an isocyanate component in a B-sided vessel; combining the resin composition, the recycled resin composition and the isocyanate component to form a reaction mixture, and discharging the reaction mixture to form a polyurethane foam article, wherein the recycled resin composition is present in the resin composition mixture in an amount of from 0.1 to 10 weight percent, based on the total weight of the resin composition mixture, and moreover, the mixture of resin compositions and the isocyanate component are combined in a mass ratio of from 0.6: 1 to 1.1: 1. 2. The method of claim 1, wherein the combining step is further defined as combining the first resin composition and the recycled resin composition to form a mixture of resin compositions and then combining the mixture of resin compositions and the isocyanate component to form a reaction mixture. 3. The method according to p. 2, in which the mixture of resin compositions has a viscosity of less than 900 centipoise at 25 ° C. 4. The method according to p. 2, in which the mixture of resin compositions has a shelf life of more than 6 months. 5. The method of claim 2, wherein the step of combining the mixture of resin compositions and the isocyanate component to form the reaction mixture is carried out in a statistical mixing head. 6. The method of claim. 1, in which the A-party and B-sided pressure vessels are less than 700 lb / ⁱⁿ² at 25 ° C. 7. The method according to one of paragraphs. 1-6, in which formic acid is present in the resin composition in an amount of from 1 to 20 weight percent, calculated on the total weight of the blowing agents included in the resin composition, and / or hydrofluoroolefin is present in the resin composition in an amount of from 30 to 95 weight percent, in terms of the total mass of pore formers included in the resin composition. 8. The method according to one of paragraphs. 1-6, in which the polyol as one component contains the first simple polyether polyol having a viscosity of less than 5000 centipoise at 25 ° C. 9. The method according to one of paragraphs. 1-6, in which the polyol as one component contains a second simple polyether polyol having a viscosity of more than 15,000 cps at 25 ° C. 10. The method according to p. 9, in which the first and second polyethers of the polyol are present in a mass ratio of from 1: 1 to 5: 1. 11. The method according to one of paragraphs. 1-6, in which the polyol as one component contains a third polyether polyol having a viscosity of less than 500 cps at 25 ° C. 12. The method according to one of paragraphs. 1-6, in which the polyol as one component contains an aromatic polyester polyol. 13. The method according to one of paragraphs. 1-6, wherein the step of discharging the reaction mixture is further defined as spraying the reaction mixture at a spray pressure of 150 to 1000 lbs / ⁱⁿ² and / or a spraying rate of 1 to 40 pounds per minute of the reaction mixture. 14. The method according to one of paragraphs. 1-6, in which the hydrofluoroolefin comprises trans-1-chloro-3,3,3-trifluoropropene. 15. The method according to one of paragraphs. 1-6, in which the product is made of polyurethane foam has a closed pore content of more than 80%.